Alkoxylation Primary hydroxyl groups

Unfortunately, it is a difference between a starter, such as nonylphenol, or a fatty alcohol, which have only one type of hydroxyl group and polyols. Some polyols used as starters for rigid polyether polyols have in the same molecule various types of hydroxyl groups (for example, primary hydroxyls and secondary hydroxyls) which do not have equivalent reactivities in the alkoxylation reactions. For example, sorbitol has two primary hydroxyls and four secondary hydroxyls, sucrose has three primary hydroxyls and five secondary hydroxyls. In both polyols, the secondary hydroxyls have different substituents and they are not totally equivalent. TMP, pentaeriythritol and dipentaerythritol have only one type of equivalent primary hydroxyl group. Thus, the initiation reaction (reaction of PO with hydroxyl groups of starter) is in fact the sum of the reactions of PO with each type of hydroxyl group of the starter ... 

Previously, it was mentioned that the steric characteristics of the carbon atom (primary, secondary, tertiary) should be considered it becomes clear with the new classes of compounds studied that the electronic characteristic of the substituent groups—aryl, hydroxyl, alkoxyl— must also be taken into account. Thus, whereas trisalkylperoxy radicals have weak recombination constants, dialkylhydroxy or dialkylalkoxy have much higher recombination constants, occasionally similar to values observed for secondary alkyl radicals. 

Lipid peroxidation may beinitiated by any primary free radical which has sufficient reactivity to extract a hydrogen atom (Fig. 2.10) from a reactive methylene group of an unsaturated fatty acid. For example, species such as hydroxyl radicals OH, alkoxyl radicals RO peroxyl radicals ROO and alkyl radicals R may be involved. The formation of the initiating species is accompanied by bond rearrangement that results in stabilization by diene conjugate formation. The lipid radical then takes up oxygen to form the peroxyl radical. Peroxyl radicals can... 

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